CN1953996A - Process and apparatus for producing olefin polymers - Google Patents
Process and apparatus for producing olefin polymers Download PDFInfo
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- CN1953996A CN1953996A CNA2005800137944A CN200580013794A CN1953996A CN 1953996 A CN1953996 A CN 1953996A CN A2005800137944 A CNA2005800137944 A CN A2005800137944A CN 200580013794 A CN200580013794 A CN 200580013794A CN 1953996 A CN1953996 A CN 1953996A
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F6/00—Post-polymerisation treatments
- C08F6/001—Removal of residual monomers by physical means
- C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
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- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
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- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00292—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant solids
- B01J2208/003—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant solids involving reactant slurries
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00761—Discharging
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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Abstract
The present invention concerns a process and an apparatus for continuous polymerisation of olefin monomers. In particular, the present invention concerns a process and an apparatus for continuous polymerisation olefin monomers like ethylene and other monomers, wherein an olefin monomer is polymerised in slurry phase in an inert hydrocarbon diluent in at least one loop reactor. According to the invention, a polymer slurry is continuously withdrawn from the loop reactor and concentrated. The concentrated slurry is conducted to a flash unit in order to remove the remaining fluid phase, and gas obtained is compressed in a flash gas compressor before it is being fed to a distillation section. By means of the present invention it is possible reduce the size of the flash gas compressor and the capacity of the distillation sections. This significantly reduces investment cost for a continuously operated polymerization apparatus.
Description
Background of invention
Invention field
The present invention relates to the polymerization of alkene.The invention particularly relates to successive polymerization olefinic monomer such as ethene and other monomer method and apparatus, wherein the slurry in the inert hydrocarbon diluent of olefinic monomer at least one loop reactor mutually in polymerization.
Description of Related Art
Loop reactor is that twentieth century grows up the fifties.Polyethylene and other olefin polymer now have been widely used for producing.In loop reactor, ethene under high pressure-temperature in the presence of hydrocarbon diluent slurry mutually in polymerization.Slurry emits and is concentrated from reactor, thereby makes the solids content of reactor exit be higher than the interior solids content of reactor.Traditionally, this finishes by sedimentation branch road (settling leg).But the existing method that concentrates loop reactor interpolymer slurry is unsatisfactory always.When in cascade reaction, producing bimodal polyethylene especially, especially like this.
Since nineteen sixties, known the outlet slurry that concentrates loop reactor with wet cyclone.The loop reactor that disposes wet cyclone is disclosed in, and for example, among the US 3 816 383, therein, take out a part of underflow and carry out the product recovery from wet cyclone, and rest part and top stream combination and return loop reactor.
The document that another piece relates to above-mentioned problem is US 4 395 523, and the document discloses the method for making and reclaim polymer beads.This currently known methods is included in polymerization in the loop reactor, and a part of circulating polymerization thing slurry is introduced wet cyclone, allows the top from wet cyclone flow back into reactor, is directed at the product recovery from wet cyclone discharging underflow and it.
In addition, EP 1 118 624, EP 1 118 625 and EP 1 118626 disclose the method for olefin polymerization, therein, polymer paste are introduced wet cyclone from loop reactor.Underflow from wet cyclone is directed to follow-up polymerization stage or product recovery.
EP 891 990 discloses the vinyl polymerization method that comprises continuous discharge polymer paste.Polymer paste constantly emits and is received in high pressure flash vessel from loop reactor.Polymkeric substance is transferred to low pressure flash vessel from high pressure flash vessel and also reclaims to product from here.
Even above-mentioned document description from the different methods of loop reactor discharging slurry, but none open or suggestion separating unit size can keep the polymerization process or the equipment that flow less than product.
Summary of the invention
The objective of the invention is the novelty of the homopolymer that will eliminate the shortcoming of prior art and production alkene, especially ethene are provided and multipolymer and economic method.
The theory that the present invention is based on is that the concentration that improved polymer paste before flash evaporation unit enters the air-flow of flash gas compressor subsequently to reduce from flasher.As everyone knows, to be led into disengaging zone, as be comprised the distilling period of heavies column and lights column from the discharging current of gas compression device.Use device of the present invention, might reduce gas compression device and the capacity and the size of distilling period subsequently greatly.
Based on above-mentioned theory, according to equipment of the present invention, with combination with preferably in the stepwise mode, comprise loop reactor, be used for improving the distilling period of heavy constituent and light constituent in device, flash evaporation unit, flash gas compressor and the recovery of polymer paste concentration of discharging self-loop reactor and the circulation flash gas compressor.The device that improves slurry concentration can be installed in outside the loop reactor.Perhaps also can link to each other, like this, when reactor emits, just can concentrate at slurry with reactor outlet.Distilling period generally comprises at least one with the stepwise form and is used for the heavies column of from the pressurized gas of flash evaporation unit separating heavy and at least one is used for isolating the lights column of light constituent from the heavy constituent top product.
According to the present invention, in loop reactor, by the slurry in hydrocarbon diluent or liquid monomer mutually at least a olefinic monomer of the polymerization method of producing olefin polymer comprise the following steps:
-constantly give off polymer paste from loop reactor,
-allow the separating device of polymer paste by polymer beads, as wet cyclone, concentrate slurry and top stream to produce,
-top stream is looped back loop reactor,
-first part is concentrated slurry loop back loop reactor,
-second section is concentrated slurry import the high pressure flash unit, being pulp separation polymkeric substance and top gas,
-reclaim polymkeric substance from flash evaporation unit,
-top of compression air-flow in the flash distillation compressor,
-allow flashed vapour through the overdraft into heavies column that circulates, from air-flow, isolating oligopolymer and other heavy constituent,
-allow and advance flasher from the circulation of at least a portion of heavies column top, with form liquid phase and vapor phase and
-at least a portion liquid phase of flasher is introduced lights column, from liquid phase, to isolate low boiling component.
According to a preferred embodiment of the present invention, the present invention is applicable to polymerising ethylene in loop reactor.
More particularly, described according to the principal character of method of the present invention characteristic as claimed in claim 1.
According to the feature of equipment of the present invention as described in the characteristic in the claim 16.
The present invention has significant advantage.Use device of the present invention, can obtain economic method, because can reduce the size of flash gas compressor.If no wet cyclone, then in the flash gas the flash vapor stream in present embodiment, comprise that also 50% flows from the top of wet cyclone.So flash streams is just bigger.Because air-flow is less among the present invention, so can reduce the size of separating unit.The present invention disposes less heavies column, lights column and comonomer tower.Less processing unit means less cost of investment.Can also realize the saving of technological operation and running cost.Energy consumption reduces because of circulating current is less.This also means more economical and eco-friendly technology.
Other details of the present invention and advantage will become clearer and more definite from the following detailed description that comprises many embodiment.
The accompanying drawing summary
Fig. 1 is the process configurations synoptic diagram of the present invention's first preferred embodiment.
Detailed Description Of The Invention
The method introduction
Reference letter and numeral used in the accompanying drawing refer to following part of appliance
A. loop reactor
B. cyclone hydraulic separators
C. flash tank
D. diluent compressor reducer
E. restructuring divides tower
F. light component tower
G. comonomer tower
H. flash vessel
With following logistics:
1. filler
2. flow to the slurry of cyclone hydraulic separators
3. second product stream
4. first product stream
5. flow from the top of flash vessel
6. through the flash gas of overcompression
7. gas flow
8. restructuring shunting
9. liquid flow
10. lower boiling flows
11. steam flow
12. underflow
13. circulation comonomer stream
14. recycle diluent stream
Therefore, as seen from Figure 1, olefinic monomer, as ethene and, randomly, one or more alpha-olefin comonomer are in the hydrocarbon diluent of loop reactor A, preferably in propane or Trimethylmethane, in the presence of polymerizing catalyst, randomly in the presence of hydrogen, carry out polymerization.
Therefore, at least a portion polymer paste of discharging like this will be imported into wet cyclone B, slurry is concentrated therein, contains first product stream 4 and main second product stream of being made up of the hydrocarbon diluent of separating from polymer paste 3 of high concentrated, solid material with generation.First product stream forms the underflow of wet cyclone B and is imported into flash evaporation unit C, and C is operation under high pressure preferably.The top stream that comprises wet cyclone second product stream loops back loop reactor A from wet cyclone B.
From flash tank, reclaim product and it is caused oven dry, stabilization and analysis.Top stream 5 is imported thinner flash distillation compressor.Allow the flash vapor stream 6 through overdraft lead to into heavies column, from air-flow 7, to isolate oligopolymer and other heavy constituent 8.Allow the air-flow 7 from heavies column lead to into flasher H, to form liquid phase 9 and vapor phase 11.At least a portion liquid phase is imported lights column, from liquid phase, to isolate low boiling component 10.Low boiling component is drawn backflash steaming device H.At least a portion vapor phase from flasher 11 is introduced the round-robin light component stream, to loop back loop reactor.
Randomly, the underflow of lights column 12 is introduced comonomer tower G.Allow and advance loop reactor A to 14 circulations of small part top stream from the comonomer tower.Randomly, what allow the comonomer tower leads to into circulation comonomer stream to small part underflow 13, advances loop reactor with circulation.
To explain each step of this method below in more detail.
A. loop reactor
In loop reactor 1, make the alkene of ethene and so on carry out homopolymerization or with at least a C
4～C
10Alpha-olefin carries out copolymerization.Polymerization occurs in inert hydrocarbon diluent or the liquid monomer, preferably at C
3～C
5In the hydrocarbon diluent, more preferably in propane or isobutane diluent, especially in the propane thinner.
Temperature in the loop reactor is about 60 ℃～about 110 ℃, preferred 75～105 ℃.If ethene or propylene carry out homopolymerization in loop reactor, then preferably under so-called " overcritical " condition, operate loop reactor, promptly service temperature surpasses the critical temperature of reaction mixture and the emergent pressure that working pressure surpasses reaction mixture.Under such condition, service temperature is higher than 90 ℃, preferably is higher than 93 ℃.
The selection of working pressure will make the material in the loop reactor or remain on liquid state, perhaps remains on above-critical state.For liquid slurry operation, the working pressure scope that is suitable for is about 20～about 100 crust, preferred 25～75 crust.For overcritical slurry operation, the working pressure scope that is suitable for is about 50～about 100 crust, preferred 55～80 crust.
Can be used for the suitable catalyst of polymerising ethylene is, for example, Ziegler-Natta catalyst, single-point catalyst, contains the multiple spot catalyzer of one or more single site catalyst components or their combination or mixture.
Ziegler-Natta catalyst comprises titanium and magnesium compound, randomly, also has aluminum compound, and can load on inert support such as silicon-dioxide or the magnesium dichloride.Preferred catalyzer be EP688 794, EP 949 274, WO 99/58584 and WO 01/55230 disclosed those.
Single-point catalyst can be any catalyzer that comprises one or more replacements or unsubstituted ring pentadienyl part.Particularly suitable be WO 97/28170 and WO 00/34341 disclosed catalyzer.
Optimal ethylene carries out (being total to) polymerization in the presence of hydrogen in loop reactor, to generate low-molecular weight polymer component.Reaction mixture generally contains 0～10%, preferred 0～4mol% alpha-olefin comonomer.If use Ziegler-Natta catalyst, then reaction mixture generally contains 2～10mol% hydrogen, preferred 2～8mol%.If use single-point catalyst, then reaction mixture generally contains 0.01～1mol% hydrogen.In addition, reaction mixture generally contains 1～10mol%, preferred 3～10mol% ethene.If use single-point catalyst, then can be with lower slightly ethylene concentration.Reaction mixture also comprises thinner composition.The major portion of preferred diluent is a propane, includes a small amount of other alkane, as methane, ethane and butane.
Polymer concentration in the reactor slurry is generally 10～40 volume %, preferred 20～30 volume %.
Polymer paste self-loop reactor emits by exporting constantly.Outlet can be positioned at any suitable position of reactor.But most preferably outlet is positioned at the suitable position in circuit cycle pump downstream.From the mode of loop reactor discharging slurry also can be to make the solids concn in exit be higher than solids concn in the loop reactor.Slurry can directly or by other enrichment step be imported into flash evaporation unit.
The pressure of reactor is controlled by the continuous blow-down of outlet from reactor by slurry.Described slurry can be imported into wet cyclone.In this case, pressure controlled valve will be placed in the product discharge tube of wet cyclone.
The performance of wet cyclone depends on the feed condition strongly.Any interference in the underflow all can influence the performance of wet cyclone.To make during design, for example, wide feed streams span of control be arranged.Then, by being looped back reactor, a part of slurry from the wet cyclone bottom reaches stable operational condition.
The particulate cut lengths can be leaned on, and for example, control enters the feed streams of wet cyclone and regulates.
The solids concn of wet cyclone bottom can be by regulating recently measuring and regulating of cycling stream (top stream) and product stream (underflow).
B. wet cyclone
Polymer paste is directed at wet cyclone B from loop reactor A, by action of centrifugal force slurry is concentrated here.Wet cyclone is divided into two strands to slurry stream: the top stream 3 and the underflow 4 that is rich in polymkeric substance that are rich in liquid.Allow and push up stream return loop reactor or enter refining holding tank (not shown), and underflow is imported into flash evaporation unit.The part underflow Huis capable of circulation road reactor.
As mentioned above, the solids content that enters the slurry of wet cyclone is 10～40 volume %.Solids concn in the underflow can be regulated with the ratio of product stream (underflow) by regulating cycling stream (top stream), is generally 30～55 volume %, preferred 40～52 volume %.Therefore solids concn generally is enhanced at least 20%, and preferably at least 50%, especially at least 100%.Make a part of underflow return loop reactor usually useful.
Maximum solids concn in the product stream depends on the restriction of stable operation.If the solids concn of slurry is too high, the danger of then stopping up product stream increases.On the other hand, be economic cause, wish that the solids concn in the slurry is high as far as possible.
That the ratio of cycling stream and product stream is generally is about 0.01～and about 10, preferred 0.01～5, more preferably 0.1～2.
The product discharge stream can freely change with the ratio of product cycling stream, so that wet cyclone and reactor all obtain stable operation.The product amount of Returning reactor can be 0～90%.
The solids concn of cycling stream is generally about 0 (or at least 0.001)～5 volume %.
C. flash evaporation unit
Flash evaporation unit C generally is made up of the flash pipe and the collector of heating.The solids concn that enters the slurry of flash evaporation unit is 30～60 volume %.In flash evaporation unit, from polymkeric substance, remove residual hydrocarbon.Flash pipe preferably heats, for example, and with steam or water.If the water heating, then hot water preferably can be taken from the chuck of loop reactor.Temperature is selected by the composition of hydrocarbon fluid, and fluid is evaporated basically." remove the fluid phase substantially " and be meant and remove most of fluid phase, only stay the volume between the filled polymer particle and the Fluid Volume of polymer particles intragranular void volume.The temperature of collector is generally 50～100 ℃, preferred 60～90 ℃, especially 70～90 ℃, and pressure be 10～30 the crust, preferred 12～27 the crust, especially 14～24 the crust.
Flash evaporation unit also can be operable to low pressure flash.This means approaching or equal and operate under the lower pressure of environmental stress.Be lower than 10 crust and preferably be lower than 5 pressure that cling to and be suitable for low pressure flash.
At least a portion will be imported into thinner compressor D from the top stream 5 of flash evaporation unit collector, to compress this air-flow.
D. heavies column
Allow the flash vapor stream 6 through overdraft lead to into heavies column, from air-flow 7, to isolate oligopolymer and other heavy constituent 8.Allow the air-flow 7 from heavies column lead to into flasher H, to form liquid phase 9 and vapor phase 11.
E. lights column,
At least a portion liquid phase 9 is imported lights column, from this liquid phase, to isolate low boiling component 10.Low boiling component is led backflash steaming device H.From flasher 11 introduce the circulation light component stream to the small part vapor phase, advance loop reactor to make it circulation.
F. comonomer tower (choosing wantonly)
Randomly, the underflow 12 of lights column is introduced comonomer tower G.Allow from the comonomer tower advance loop reactor A. randomly to 14 circulations of small part top stream, what allow the comonomer tower leads to into circulation comonomer stream to small part underflow 13, advances loop reactor with circulation.
Slurry reactor according to the present invention's operation can be included in the multistage polymerization sequence, described sequence comprises one or several slurry reactors, they are connected with one or several gas-phase polymerization reactors, common pending application application EP 02396161.8 as us is disclosed, and its content is drawn in this for reference.
In content of the present invention, point out that briefly Gas-phase reactor can be operated under preferred 70～110 ℃ temperature at about 60～about 115 ℃.Working pressure is 10～30 crust, preferred 15～25 crust.In Gas-phase reactor, alkene and one or more C
2～C
10Alpha-olefin comonomer is carried out copolymerization, or the alkene of ethene and so on carries out homopolymerization.The copolymerization in containing the Gas-phase reactor of a small amount of hydrogen of the alkene of optimal ethylene and so on is to generate the High molecular weight polyethylene multipolymer.Reaction mixture generally contains 5～25mol% ethene, 0.1～10mol% alpha-olefin comonomer and 0.01～3mol% hydrogen.If come polymerising ethylene with single-point catalyst, then hydrogen richness can be 0.001～1mol%.All the other are made up of inert component such as nitrogen or propane.
Following indefiniteness embodiment illustrates the present invention.
Embodiment
Embodiment 1:
Operation contains the 10m of propane thinner under 95 ℃ and 60 bar pressures
3Loop reactor.It is as follows to produce Alathon in reactor: introduce ethene, thinner, hydrogen and polymerizing catalyst, described catalyzer is pressed the method preparation of embodiment 3 among the EP 688794, but with average particle size particle size be the silicon-dioxide of 20 μ m as solid support material, the consumption of raw material will make thinner contain 5.9mol% ethene and 2.6mol% hydrogen.All the other be propane and a small amount of methane, ethane, Trimethylmethane and normal butane (each＜1mol%).Polymer yield is 1.4t/h, and the melt index of polymkeric substance is that 450g/10min and density are 973kg/m
3The solids content of slurry is 25 volume %.
According to Fig. 1, polymer paste is constantly emitted and transfers to wet cyclone from reactor by outlet nozzle.The slurry total amount of inserting wet cyclone is 5.5t/h.Product stream is 3.7t/h, contains 52 volume % solids.Cycling stream is 1.8t/h, contains 1.7 volume % solids.Allow cycling stream return loop reactor.Product stream is divided into two strands: the product discharge stream is about 1.8t/h, and the product cycling stream is about 1.9t/h.The product discharge stream was introduced except that the hydrocarbon stage, and allowed the product cycling stream return into loop reactor.
Allowing the product discharge stream of wet cyclone enter service temperature via heating tube is that 70 ℃ and pressure are the flash tanks of 20 crust.Allow the hydrocarbon of from polymkeric substance, separating through the speed return loop reactor of diluent recovery with 0.3t/h.They contain 5.9mol% ethene and 2.6mol% hydrogen.
Polymkeric substance is caused product reclaims, with dry, stabilization and analysis.
This embodiment illustrates that how economical present method is: if there is not wet cyclone, then also comprise the about 50% top stream from wet cyclone the flash vapor stream of flash vapor stream in comprising this embodiment.Therefore flash gas stream is exactly 0.5*1.8t/h+0.3t/h=1.2t/h.
Embodiment 2:
In the reactor of embodiment 1, introduce ethene, 1-butylene, hydrogen and thinner and the similar catalyzer used, make reaction mixture contain 6.8mol% ethene, 3.1mol%1-butylene and 1.8mol% hydrogen with embodiment 1.Polymerization temperature is 85 ℃.Polymer yield is 1.2t/h, and the melt index of polymkeric substance is that 200g/10min and density are 950kg/m
3The solids content of slurry is 25 volume %.
According to Fig. 1, polymer paste is constantly emitted and transfers to wet cyclone from reactor by outlet nozzle.The slurry total amount of inserting wet cyclone is 5.2t/h.Product stream is 3.8t/h, contains 39 volume % solids.Cycling stream is 1.4t/h, contains 5.8 volume % solids.Allow cycling stream return loop reactor.Product stream is divided into two strands: the product discharge stream is about 1.9t/h, and the product cycling stream is about 1.8t/h.The product discharge stream was introduced except that the hydrocarbon stage, and allowed the product cycling stream return into loop reactor.
Allowing the product discharge stream of wet cyclone enter service temperature via heating tube is that 70 ℃ and pressure are the flash tanks of 20 crust.Allow the hydrocarbon of from polymkeric substance, separating through the speed return loop reactor of diluent recovery with 0.6t/h.They contain 6.8mol% ethene, 3.1mol%1-butylene and 1.8mol% hydrogen.
Polymkeric substance is caused product reclaims, with dry, stabilization and analysis.
Claims (24)
1. in loop reactor, produce the method for olefin polymer, the slurry of wherein at least a olefinic monomer in hydrocarbon diluent or liquid monomer mutually in polymerization, described method comprises:
-middle mutually at least a the monomer of polymerization of slurry in loop reactor,
-from the continuous polymer discharge slurry of loop reactor,
The concentration of-raising polymer paste,
-top stream is circulated to loop reactor,
-first part is concentrated slurry loop back loop reactor,
-second section is concentrated slurry import flash evaporation unit,
-reclaim polymkeric substance from flash evaporation unit,
-compression first part overhead gas stream in the flash distillation compressor,
-make the compressed flashed vapour into heavies column that circulates, from air-flow, isolating oligopolymer and other heavy constituent,
-make from the circulation of the second section of heavies column top and advance flasher, with form liquid phase and vapor phase and
-at least a portion liquid phase is introduced lights column, from liquid phase, to isolate low boiling component.
2. according to the process of claim 1 wherein that at least a portion underflow of lights column is imported into the into recycle diluent stream of loop reactor that will circulate.
3. according to the method for claim 1 or 2, wherein at least a portion vapor phase of flasher is imported into the into circulation light component stream of loop reactor that will circulate.
4. according to the method for claim 1, wherein the underflow of lights column is introduced into the comonomer tower and is introduced into loop reactor from least a portion top stream of comonomer tower, and at least a portion underflow of comonomer tower is introduced into circulation comonomer stream, advances loop reactor with circulation.
5. according to any one method in the aforementioned claim, the solids content that wherein concentrates slurry is 30～55%, preferred 40～52 volume %.
6. according to any one method in the aforementioned claim, wherein 10～90% concentrate slurries and be recycled loop reactor and second section and concentrate slurry and be conducted to flash evaporation unit.
7. according to any one method in the claim 1～6, wherein slurry is concentrated in wet cyclone, comprises the underflow that concentrates slurry and the top stream of rich hydrocarbon with generation.
8. according to any one method in the claim 1～7, wherein the method from loop reactor discharging slurry will make the solids concn in exit greater than the solids concn in the loop reactor.
9. according to the method for claim 8, wherein top stream is recycled loop reactor.
10. according to the method for claim 9, wherein round-robin top stream is 0.01～10 with ratio from the underflow of wet cyclone discharging, and is preferred 0.01～5, especially 0.1～2.
11. according to any one method in the claim 8～10, wherein the solids content of slurry is 0.001～5 volume % of this stream in the stream of top.
12. according to any one method in the aforementioned claim, wherein flash evaporation unit comprises flash pipe and collector, described flash pipe randomly heats, concentrate remaining hydrocarbon to the small part of slurry therein and flash to the top stream that contains the evaporative fluid phase, formation contains the top stream of evaporative fluid phase and contains polymer beads and small volume of fluid product stream mutually in described collector.
13., wherein contain and be less than 0.1mol% hydrogen from the product stream of flash evaporation unit according to any one method in the aforementioned claim.
14. according to any one method in the aforementioned claim, wherein monomer is an ethene, it randomly with one or more C
4～C
10Alpha-olefin copolymer.
15. according to any one method in the aforementioned claim, wherein catalyst system comprises Ziegler-Natta catalyst, single-point catalyst, multiple spot catalyzer or their combination or mixture.
16. produce the equipment of olefin polymer in the presence of catalyst system, this equipment comprises:
-loop reactor,
-improve from the solids concn of the slurry of loop reactor discharging producing the device that concentrates slurry,
-flash evaporation unit is used for making in the agent of slurry phase dilution all remaining hydrocarbon liquid phases to evaporate substantially, contains the gas/solid mixture of polymer solids and gas with generation.
-flash gas the compressor that links to each other with flash evaporation unit outlet, be used for compressing in the flash evaporation unit at least a portion top gas body and
-distilling period, be used for reclaiming and the flash evaporation unit top gas body that circulates in weight and light constituent.
17. according to the equipment of claim 16, the device that wherein is used for improving slurry solids content comprises wet cyclone.
18. according to the equipment of claim 16 or 17, wherein distilling period links to each other with the outlet of flash gas compressor.
19. according to any one equipment in the claim 16～18, wherein distilling period comprises at least one heavies column that is used for isolating heavy constituent from the pressurized gas of flash evaporation unit in the stepwise mode and at least one is used for isolating the lights column of light constituent from the apoblema of heavy constituent top.
20., comprise the combination of following parts according to any one equipment in the claim 16～19:
-loop reactor, be used for making olefinic monomer reaction mixture slurry mutually in polymerization, described reaction mixture comprises fluid hydrocarbon and optional hydrogen and polymer beads, and at least one outlet is arranged on the reactor, allowing continuous polymer discharge slurry,
-at least one wet cyclone, on first outlet of the inlet of at least one polymer paste and at least one concentrated slurry and second outlet of at least one top stream are arranged, described inlet links to each other with the outlet of loop reactor, and described wet cyclone is used for isolating fluid to produce concentrated slurry from polymer paste
-flash evaporation unit, on first outlet of suspensoid of the inlet of at least one slurry and at least one polymer solids and gas and at least one evaporative fluid second exporting mutually arranged, described inlet links to each other with first outlet of wet cyclone, and described flash evaporation unit is used for isolating the fluid phase from concentrate slurry
-flash gas compressor links to each other with second outlet of flash evaporation unit, is used for compressing at least a portion top gas in the flash evaporation unit, is useful on the outlet of compression flash gas on the described compressor,
-at least one is used for the heavies column of separating heavy, have second of first outlet of the inlet of a pressurized gas that links to each other with the compressor outlet and a top product and bottoms to export on it and
-at least one lights column links to each other with first outlet of heavies column, is used for isolating from top product light constituent.
21., also comprise a comonomer tower that links to each other with the outlet of lights column underflow according to any one equipment in the claim 16～20.
22. according to any one equipment in the claim 16～21, wherein the comonomer tower comprises the outlet of a top stream, this outlet links to each other with the circulating line of loop reactor.
23. according to any one equipment in the claim 16～22, wherein flash distillation is a high pressure flash.
24. according to any one equipment in the claim 16～23, wherein the outlet of loop reactor is positioned the appropriate location in circuit cycle pump downstream.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04396032.7 | 2004-04-29 | ||
| EP04396032A EP1591459B1 (en) | 2004-04-29 | 2004-04-29 | Process and apparatus for producing olefin polymers |
| PCT/FI2005/000202 WO2005105862A1 (en) | 2004-04-29 | 2005-04-29 | Process and apparatus for producing olefin polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1953996A true CN1953996A (en) | 2007-04-25 |
| CN1953996B CN1953996B (en) | 2011-10-19 |
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|---|---|---|---|
| CN2005800137944A Active CN1953996B (en) | 2004-04-29 | 2005-04-29 | Process and apparatus for producing olefin polymers |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7740808B2 (en) |
| EP (1) | EP1591459B1 (en) |
| CN (1) | CN1953996B (en) |
| AT (1) | ATE331740T1 (en) |
| BR (1) | BRPI0510389A (en) |
| DE (1) | DE602004001391T2 (en) |
| EA (1) | EA010813B1 (en) |
| ES (1) | ES2268605T3 (en) |
| SA (1) | SA05260111B1 (en) |
| WO (1) | WO2005105862A1 (en) |
| ZA (1) | ZA200609520B (en) |
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| CN102190742A (en) * | 2010-03-17 | 2011-09-21 | 中国石油化工股份有限公司 | Olefin polymerization device and olefin polymerization method |
| CN102037021B (en) * | 2008-05-20 | 2013-01-02 | 英尼奥斯制造业比利时有限公司 | Olefin polymerisation process |
| CN103459440A (en) * | 2011-04-12 | 2013-12-18 | 切弗朗菲利浦化学公司 | System and method for processing reactor polymerization effluent |
| CN103857709A (en) * | 2011-12-19 | 2014-06-11 | 博里利斯股份公司 | Loop reactor providing an advanced production split control |
| CN108623719A (en) * | 2018-04-13 | 2018-10-09 | 武汉科技大学 | A kind of gas-lifting type olefinic polymerization device and polymerization |
| CN109715675A (en) * | 2016-09-21 | 2019-05-03 | 博里利斯股份公司 | Method for the separate hydrocarbon from polymer |
| CN112745185A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for continuously producing alpha-olefin by ethylene oligomerization |
| CN112745179A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for producing alpha-olefin by ethylene oligomerization |
| CN113260642A (en) * | 2018-12-27 | 2021-08-13 | Sabic环球技术有限责任公司 | Process for preparing polyethylene |
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| EP1825910A1 (en) * | 2006-02-24 | 2007-08-29 | Total Petrochemicals Research Feluy | Method for transforming a loop reactor |
| ATE509041T1 (en) * | 2006-05-22 | 2011-05-15 | Borealis Tech Oy | METHOD FOR PRODUCING POLYOLEFINS WITH EXTRA LOW IMPURITIES CONTENT |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6239235B1 (en) * | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
| ES2349631T5 (en) * | 2002-09-16 | 2018-05-04 | Chevron Phillips Chemical Company Lp | Procedure and system for removing heavy materials from the recirculated diluent to a suspension polymerization reactor |
-
2004
- 2004-04-29 AT AT04396032T patent/ATE331740T1/en not_active IP Right Cessation
- 2004-04-29 DE DE602004001391T patent/DE602004001391T2/en not_active Expired - Lifetime
- 2004-04-29 ES ES04396032T patent/ES2268605T3/en not_active Expired - Lifetime
- 2004-04-29 EP EP04396032A patent/EP1591459B1/en not_active Expired - Lifetime
-
2005
- 2005-04-27 SA SA05260111A patent/SA05260111B1/en unknown
- 2005-04-29 BR BRPI0510389-4A patent/BRPI0510389A/en not_active IP Right Cessation
- 2005-04-29 CN CN2005800137944A patent/CN1953996B/en active Active
- 2005-04-29 US US11/578,138 patent/US7740808B2/en active Active
- 2005-04-29 WO PCT/FI2005/000202 patent/WO2005105862A1/en active Application Filing
- 2005-04-29 EA EA200602001A patent/EA010813B1/en not_active IP Right Cessation
-
2006
- 2006-11-16 ZA ZA200609520A patent/ZA200609520B/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| DE602004001391T2 (en) | 2007-05-31 |
| WO2005105862A1 (en) | 2005-11-10 |
| EA010813B1 (en) | 2008-12-30 |
| EP1591459B1 (en) | 2006-06-28 |
| ES2268605T3 (en) | 2007-03-16 |
| BRPI0510389A (en) | 2007-11-13 |
| DE602004001391D1 (en) | 2006-08-10 |
| ATE331740T1 (en) | 2006-07-15 |
| EA200602001A1 (en) | 2007-02-27 |
| SA05260111B1 (en) | 2008-11-17 |
| US20080039597A1 (en) | 2008-02-14 |
| EP1591459A1 (en) | 2005-11-02 |
| US7740808B2 (en) | 2010-06-22 |
| CN1953996B (en) | 2011-10-19 |
| ZA200609520B (en) | 2008-06-25 |
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